CA1100124A - Silicone lubricant composition - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The present invention relates to a silicone lubricant composed of an organopolysiloxane polymer and an effective amount of chlorinated phosphite or phosphonate. Such a lubricant composition is especially effective for lubricat-ing soft metals such as copper or bronze and for improving dimethylpolysiloxane lubricants.

Description

~ 60SI-121 LZ~
The present invention relates to a silicon lubricant composition and more specifically the present invention relates to a silicone lubricant composition for lubricating hard metal surfaces or soft metal surfaces such as copper or bronze.
Silicone lubricants are well known for hard metal surfaces. Such silicone lubricants usually comprise an organopolysiloxane polymer which may be dimethylpoly-siloxane polymer, a methyl, higher-alkyl substituted poly-1 ~ siloxane polymer-~ chlorophenyl or tetrachlorophenyl sub-stituted polysiloxane polymer. Also, there are silicone lubricants in which the base lubricating fluid is composed of a trifluoropropyl substituting organopolysiloxane polymer.
These fluids may be utilized by themselves or with various other additives for the lubrication of metal surfaces. For instance methyl, higher-alkyl substituted organopoly-siloxane polymers are very effective for lubricating hard metal surfaces. In addition dimethylpolysiloxanes with ~arious chlorinated additives are also known for lubricating hard metal surfaces such as for instance disclosed in Agens U.S. Patent No. 2,837,482 dated June 3, 1958. Such chlorinated additives are described in the foregioing Agens Patent consist of octyltetrachlorobenzoate, dioctyl-tetrachloro-phthalate and bis-2-ethylhexyl tetrachlorophthalate. In addition various types of chlorinated phthalates car, be utilized as additives for dimethylpolysiloxanes such as bis-2-al~ylhexyltetrachlorophthalates. In these compounds the alkyl may contain anywhere from 2 to 8 carbon atomsc As one examp]e for instance the methyl~ higher-alkyl substitu-ted polysiloxanes have been shown to be effective as a lub-ricant for hard metals or any metal if they have a film thickness three times the surface roughness which for most .

hard metal surfaces would require Eilm thickness of 30 ~o 45 micro inches. Most silicone lubricants and specifically methyl, higher-alkyl substituted polysiloxanes have a film thickness from 20 to 30 micro inches. Accordingly, what happens with hard metals is that the methyl higher-alkyl substituted polysiloxanes allows a slow attrition of the asperities in the metal surface and an improvement of the metal surface to a roughness of 5 micro inches which depth of surface roughness can be handled by the methyl higher-alkyl substituted polysiloxanes to lubricate such hard metal surfaces. For dimethylpolysiloxanes which are not as effective as the methyl higher-alkyl substituted poly-siloxanes in lubricating metal surfaces, it is necessary to also add a chlorinated additive. Conventional chloride additives may also be added to methyl tetrachlorophenyl substituted polysiloxanes to form ferrous chloride hydrate compounds at the surface of the hard metal which is being lubricated so that the oxy chloride will shear off under stress and prevent undue wear against the hard metal surface.
Accordingly in summary, it has been found out that methyl higher-alkyl substituted polysiloxane with or without additives will function in most cases as an effective lubricant for hard metals the dimethylpolysiloxane lubricants will function as lubricants for hard metals with the addition of chloride additives and that tetrachlorophenyl substituted polysiloxanes will function to some extent wikhout additives in lubricating hard metal surfaces but will ~unction most effectively with the use of chlorinated additives in the lubrication of hard metal surfac~es. The reason the dime-thylpolysiloxane polymers and the tetrachlorophenyl sub-stituted polymers need the additives, is that they do not form as an effective thickness of film on the hard metal : ' .. ' ..

surfaces as is possible with the methyl higher-alkyl sub-stituted polysiloxanes. However, all of these oryano-polysiloxane lubricants as well as others tha-t haven't been mentioned above with or without the tra~itional chlorinated additives have a serious deficiency when it comes to lubrica-ting soft metals, such as brass, bronze, soft steel, free machining steel, lead, copper etc. In the case where the organopolysiloxane polymers are applied to lubricate soft metals, the wear rate is initially low and a low sliding friction prevails then after a short period of low wear a very high rate wear is experienced with a sizable increase in the sliding friction causing the metal parts to wear away at a higher rate.
It should also be pointed out that such chlorina-ted additives such as those of the ~gens Patent are not as effective as would be desired even with silicone polymers in lubricating soft metals. When silicone lubricants are applied to lubricate soft metal, even in the case with methyl higher-alkyl substituted polysiloxanes that such prior chlorinated additives have to be utilized at very high concentrations of 4 to 10% by weight of the lubricating composition to effect any sizable change in the performance of the lubricant composition. Accordingly, it was highly desirable to be able to formulate an additive which could be utilized at small concentrations for addition to silicone polymers to prepare silicone lubricant compositions for the lubrication of soft metals. It was desired that such silicone lubricant with the additive in it would form oxychloride compounds on the soft metal surface and the 3Q_~ soft metal being in contact with another soft metal or - ~ even a hard metal would ~ the oxychloride compounds to shear off thus protecking the soft metal surface from wear.

~ 60S~ 121 . .~ ~

Prior art chloride additives needed to be utilized at high concentration as addi-tives to silicone lubricants, since they were not very efficient in forming oxy chloride compounds at the point of wear.
- Accordingly, it was thought it would be highly advantageous to obtain some type of chlorinated additive for such silicone lubricant which would form the appropriate type of oxychloride compounds which were needed for soft metal surfaces such as copper and bronze. Then the oxych-loride compounds would be sheared off instead of the soft metal and allow the soft metal to wear gradually and not at a high rate as was experienced previously. Accordingly, it was highly desirable to formulate and obtain an additive for silicone polymers utilized in forming lubricant compositions which such additive would decrease the wear of hard metal surfaces but would more importantly decrease the wear of soft metal surfaces when they acted upon each other or when a soft metal surface acted against a hard metal surface. It should be noted that the foregoing discussion a~ove as to the formation of oxychloride com-pounds at the surfaces of the metals and the function of A~
such compounds preventing undue~r is a theoretical discussion.
In summary, what was needed was chlorinated additive or other type of additive for polysiloxane polymers that could be utilized as a~ lubricant to decrease the wear of metal surfaces acting against each other, which was much more efficient that the prior art organopolysiloxane poly-mers with various additives such as those instance dis-,- ~
closed in the foregoing Agens U.S. Patent No.2,837,482 dated June 3, 1958.
Accordingly, it is one object of the present invention .~ .

to provide for an addltive for s.ilicone lubricants which would decreases the wear of hard metal surfaces lubricated by such silicone polymers.
It is another object of the present invention to provide an additive for a silicone lubricating composition which would decrease the wear when such silicone lubricants was utilized to lubricate soft metal surfaces.
There is an additional object of the present invention to provide for an additive for a silicone lubricant com-position which would decrease the wear when such lubricant composition was utilized to lubricate soft or hard metal surfaces acting against each other.
It is yet an additional object of the present in-vention to provide for a silicone lubricant composition which has excellent lubricity properties for lubricating -copper, bronze, and brass surfaces. These and other objects of the instant invention are accomplished by the means of the disclosure set forth herein below.
In accordance with the above object~ there is provided hy the present invention a silicone lubrican-t composition comprising 100 parts by weight of an organopolysiloxane polymer having a viscosity varying from S0 to 50,000 centi-poise wherein the organo groups are selected from the class consisting of monovalent hydrocarbon radicals and halo-genated hydrocarbon radicals wherein there is added to the composition in an effective amount of a chlorinated phos- .
phite or phosphonate and more specifically from .01 to 1 part by weight of a chlorinated phosphite or phosphonate.
The most preferred phosphites and phosphonates for use in ~ 30 the instant composition is trischlorethylphosphite and : bis chloroethyl phosphonate. Although, the instant ad-ditives may be utilized in trace~ amoun~ as is desired for ; 60SI-121 any type of silicone lubricant composition. It is most specifically suited for addition to lubricant compositions where the basic polymer is a dimethylpolysiloxane polymer or an organopolysiloxane polymer with the organo groups selected from methyl, tetrachlorophenyl or trifluoropropyl or from a methyl, high-alkyl subs-tituted polysiloxane polymer.
The additive may be utilized by itself or in combination with the well known chlorinated aaditives of the fore~
going Agens Patent. For methyl, higher-alkyl, and tet-rachlorophenyl substituted polysiloxanes the chlorinatedadditives of the foregoing Agens Patent are not needed. In the case of dimethylpolysiloxanes, the chlorinated additives of the foregoing Agens Patent should be added along with the phosphites and phosphonates of the instant case for optimum efficiency while the additives of the instant '! invention are disclosed primarily for the lubricating of soft metals that is where either of the two surfaces are soft metals it can also be utilized with advantage with ` hard metals, such as machine steel, tool steel, etc. The preferred soft metals in which the present lubricant composition can be used with repsect thereto are for instant ; copper, brass, bronze, lead, tin and other soft metal sur-faces, soft steel, machine steel, aluminum, etc. It should be noted while the instant case discloses only the use of two specific phosphites or phosphonates any highly chlorinated phosphites or with substitution which are soluble ln *he organopolysiloxane base polymer as described above may be utilized as additives in accordance with the invention. For some reason which is not known the phosphite or phosphonate ~ =3~ activates the chlorinated part of the molecules, allowing it to form compounds at the surface i~ of the soft metal, as it has been theoretically discussed ~ - 6 -:
,~ . . , ~ 60SI-121 discussed above. However they perform their function, it has been found that the instant additives even in trace amounts do effectively decrease the wear for soft metal surfaces.
Phosphite and phosphonate lubricant addi-tives can be added to any silicone lubricant or any silicone polymer which is utilized as a lubricant to improve the lubricating properties of the silicone polymer. Preferably such poly-siloxanes may be any organopolysiloxane where the organo to ~ ratio may vary from 1.9 to 2.57 and where the organo groups are selected from monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals. Accord-ingly while i-t is preferred that such silicone polymer be a linear polymer or essentially a linear diorganopoly-siloxane polymer, nevertheless, they may be up to 10% in such linear diorganopolysiloxane polymer of monofunctional siloxy unit or trifunctional siloxy units. Most preferably, the organopolysiloxane polymer is one embodiment of the instant invention is a linear polysiloxane and more specifi-cally a linear diorga~opolysiloxane polymer where the organo to Si ratio varies from 1.9 to 2.01, where the organo groups are selected from monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals, and the polymer has a viscosity that varies anywhere from 50 to 50, 000 centipoise at 25C. Generally the polymer - may have a viscosity that may vary anywhere ~rom 25 or 50 to-100,000 centipoise viscosity at 25C, but more prefer-ably the polymer has a viscosity that varies from 50 to 5G,000 centipoise at 25~C. The above specificities with respect to the organopolysiloxane polymer apply to any of the preferred organopolysiloxane polymers that will be described below or that have been described above for , ~ .

~ 6OSI-121 utilization as the basic silicone lubricant polymer of the instant invention. Such organo substituent groups of such polymers may generally be selected from monoyalent hydro-carbon radicals and halogenated monovalent hydrocarbon radicals such as, alkyl radicals, methyl, ethyl, propyl;
higher alkyl radicals such as, decyl, dodecyl and etc., mononuclear aryl radicals such as, phenyl, methylphenyl, ethylphenyl; cycloalkyl radicals such as, cyclohexyl, cycloheptyl, and etc., halogenated monovalent hydrocarbon radicals such as, chlorophenyl, tetrachlorophenyl and ~ -trifluoropropyl and various other radicals and substituent groups for utilization in the polymers of the instant case which are well known and established as organic sub-stituent groups in silicone polymers. One preferred lubricant for utilization in the instant case is where the organo substituent groups in the diorganopolysiloxane polymer are methyl such as a dimethylpolysiloxane polymer of a viscosity anywhere from 25 centipoise to 100,000 centipoise or more preferably of a viscosity of 30 centi-poise to 50,000 centipoise at 25C. Although such a polymer may have some phenyl substitution, in the most preferably form it does not have any phenyl substitution. Of course, as mentioned, the above does not apply to chlorophenyl or tetrachlorophenyl substituent groups since in anothPr preferred embodiment of the instant case, the linear diorganopolysiloxane polymer has a minor amount of chloro-phenyl or tetrachlorophenyl substituent groups along with methyl substitu~nt groups.
The dimethylpolysiloxane polymer is utilized as a 30 Iubricant in accordance with the instant invention to which the phosphite and phosphonate additives of the instant case are applied. It is also preferred to utilize 1 to 10 parts . . : . ~ . . ...... ... , : . ,, :
:: : : . . . .... ... . .

i I
L~'~ t by weight of chlorinated benzoate or chlorinated phthalate as disclosed in the foregoing Agens U.S. Patent No.2,837,482 dated June 3, 1958, in addition to the phosphite and phos-phonate additives of the instant case. Such concentrations of the chlorinated phthalate or chlorinated benzoate are added per 100 parts of the linear diorganopolysiloxane polymer.
It has been found in accordance with the instant invention that the lubricating compositions of the instant case have the ma~imum lubricating properties when there is added to such linear diorganopolysiloxane polymers and specifically linear dimethylpolysiloxane polymers, the foregoing chlori-nated benzoates and chlorinated phthalates in addition to the phosphite and phosphonate additives of the instant case. Generally, it is not desired to add more than 10 ~` parts of the henzoate or phthalate since more than 10 pa~ts is not soluble in the linear dimethylpolysiloxane polymer and less than 1 part does not add any appreciable anti-properties to the lubricating composition in com-bination with the phosphite and phosphonate additives of the instant case. Generally such chlorinated addi-tives such as that disclosed in the foregoing Agens Patent,can be any highly chlorinated benzoate or highly chlorinated phthalate, and specifically tetrachlorinated benzoate or tetrachlorinated phthalates. Specific preferred additional additives of the foregoing Agens Patent for utilization in the lubricating compositions of the instant case are, for instance, octyltetrachlorobenzoate, diacty-ltetrachlorophthalate, bis-2-ehtylhexyltetrachloroptha-late and bis-~-butylheY.yltetrachlorophthalate. Generally with respect to the phthalates, any bis-alkylhe~yltet-rachlorophthalate may be utilized as an additive in the instant case to provide for lubricating compositions with _ g _ r .~ . . . ~ ~ . .
. . '. . ' ' ., ', ' ' . ", ~

enhanced lubricating properties and antiwear properties for soft metals as well as for hard metals.
.~ It should be noted that basically any of the linear organopolysiloxane polymers of the instant case may be utilized with the foregoing chlorinated phthalates and benzoates with impxoved antiwear properties for hard metals.
However, such chlorina~ed benzoates and phthaltes are effective for adding or imparting antiwear properties to silicone lubricants for soft metals only at high con-centrations. However, these chlorinated benzoates and phthalates are disclosed in the instant case as additives to silicone lubricant compositions in combination with the phosphites and phosphonates of the instant case, especially in the case of linear dimethylpolysiloxane polymers.
In the case where the silicone lubricant polymer is a linear methylchlorophenyl or tetrachlorophenyl sub-stituted polysiloxane polymer within the above viscosity ambients then the foregoing chlorinated benzoates and phthalates may or may not be utilized as additives. Most preferably they are utilized as additives in combination with the phosphites and phosphonates of the instant case : to impart to them optlmum antiwear properties for soft metals for the lubricating compositions of the instant case.
; In the case of mèthyl, high-alkyl substituted linear polysiloxane polymers such chlorinated benzoates and phthalates are not needed as antiwear additives when the silicone lubricant composition compased of such methyl higher-alkyl polymer is utilized to lubricate either ~ soft or hard metals. With the methyl higher-alkyl poly-.~ siloxane silicone lubricant compositions only the phosphite .

: , , .

~ 60SI-121 and phosphonates of the ins-tant case are needed to impart or improve the lubricant composition such that it has optimum antiwear properties when it is utilized to lubricate soft or hard metals. In any case, as disclosed in the instan-t cae, the chlorinated benzoate and the chlorinated phthalate additives of the foregoing Agens patent may be utilized with advantage with cer~ain linear diorganopoly~
siloxane silicone lubricant compositions as may be desired.
At any rate, such additives do not produce any harmful effects when they are added to silicone lubricant com-positions and are certainly advantageously added to the linear dimethylpolysiloxane silicone lubricant compositions, so as to optimize the antiwear properties of such polymers.
The linear diorganopolysiloxane polymers may be produced by any method that is well known in the art. For instance, in the case of polysiloxanes substituted by methyl and phenyl units, polysiloxanes substituted by chlorophenyl~
tetrachlorophenyl and methyl units and polysiloxanes substituted by methyl and trifluoropropylsiloxane units, such polymers may be prepared by the equilibration of the appropriate cyclotetrasiloxanes with the appropriate amount of chain-stoppers such as, hexamethyldisiloxane, octamethyltrisiloxane and etc. In the presence of an ~ acid catalyst such as, toluene sulfonic acid, acid activated ,, .~ ~
clay such as, Filtrol manufactured and sold by the Filtrol of Los Angles, California, and etc. The amount of chain-stopper in the equilibration mixture will determined the final molecular weight of the equilibrated polymer (usually , ~ the equilibration is stopped when ~5~ of the cyclicpoly ~ -siloxanes has been converted to a linear polymer). At that time the equilibration which is carried on at elevated temperatuxes of about 100 C is simply terminated by lower-; ~
,, . , ~. .

~ 60SI-121 ing the temperature and venting off the excess cyclic material. In the case of the linear diorganopolysiloxane polymer that is to be composed of methyl and trifluor-propyl units, either the appropriate cyclictrisiloxane or tetracyclicsiloxane may be utilized in the equilibration reaction as is well known in the art. In any case whether cyclictrisiloxanes or cyclicsiloxanes are utilized in the instant case depends on the choice or skill of the worker in the art in his experience with a particular type of reaction. AS an example of a process for producing such methyltrifluoropropyl cyclicsiloxanes and producing a polymer therefrom, reference is to the U.S. Patent No.
3,937,684 dated February 10, 1976.
The methods for producing such linear diorganopoly-siloxane polymers with various substituent groups is well known in the art and as such will not be repeated here in detail. Another preferred linear diorganopolysiloxane polymer for utilization as to basic lubricant in the invention of the instant case for soft metals with the additives of the instant case is a linear polysiloxane polymer having methyl and tetrachlorophenyl substituent groups. Such polymer is, for instance, disclosed for use as a lubricant in U.S. Patent 2,970,162 - Brown dated January 31, 1961.
Accordingly, it will TlOt be necessary to go into preparation of such materials or disclosure. Suffice to say that such linear diorganopolysiloxane polymer substituted by methyl and tetrachlorophenyl substituent groups are well known. It was the discovery of the instant case that the utilization of the chlorinated phosphites and phosphonates of the instant case would improve such lubricants when they were utilized to lubricate soft metals such that the antiwear properties of such silicone lubricants are superior ~ 60SI-121 to that of the priot art.
Finally, there can be utilized as a preferred lubricant fluid in the lubricating composition of the inskant case, a methyl higher-alkyl linear polysiloxane of a viscosity as set forth previously. Preferably the higher-alkyl group in such linear polysiloxane polymer has from 6 to carbon atoms and is more preferably decyl, dodecyl and etc. Such polysiloxane polymer is linear except that each silicone atom has a substituent selected from methyl and also has a substitute selected from a higher-alkyl radical where the carbon atoms are the high-alkyl substituted groups in the linear polysiloxane polymer varies from 25 to 50 mole percent of the total substituent groups on the polymer.
Such higheralkyl polysiloxane polymers are generally produced by reacting a hydrogen-containing linear polysiloxane poly-mer, which can be produced by the foregoing equilibration techniques set forth previously, with an olefinic 6 to 20 carbon atom organic molecules such that the olefinic organic molecule is added on the hydrogen atom of the polysiloxane to yield the methyl higher-alkyl substituted linear polysiloxane which may be utilized as a preferred lubricant in the instant case.
With respect to the production of the hydrogen poly-siloxane, as stated previously, such hydrogen polysiloxanes may be produced by equllibration techniques along the line that is utilized for the methyltrifluoropropyl substituted polysiloxanes or the dimethyl substituted polysiloxanes.
It should also be noted that such cyclictetrasiloxanes and cyclictrisiloxanes as needed in the foregoing equilibration processes, are easily produced by the hydrolysis of the appropriate dichlorosilanes and specifically such silanes as dimethyldichlorosilane, and methyltrifluoropropyldich-... .

ql`1.24L 6 o s I- 121 lorosilane. By hydrolyzing such chlorosilanes in water there , is obtained a mixture of cyclic and low molecular weight linear polysiloxanes and the cyclic material is increased in concentraticn and stripped off in fairly pure quantities by simply cracking the hydrolyzate with an alkali metal hydroxide at elevated temperatures.
With respect to the fluid methyl higher-alkyl polysiloxanes, one such preferred methyl, higher-alkyl polysiloxane -that can be employed in the practice of the present invention can be charac-terized as having the average unit formula, ~,. 3)n(R)m(R (CEI2)3)p(R~)qSiO(4 The sum (m+n+P+q) has a value of from 2.002 to 3.0; n has a value of from 0.50 to 1.95; m has a value of from 0.50 to loOO; p has a value of from O to 0.5; q has a value of ~rom O to one-fourth ; (m+n+p); R is an alkyl radical containing from six to 20 carbonatoms; e.g.; hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl radicals; R' is a t-butyl-substituted hydroxyaryl radical and has ` the formula:
.:

Y ~ - OH

where Y is a memher selected from the class consisting of hydrogen, monovalent hydrocarbon radicals, hydroxyaryl radicals~ hydroxy-aryl-substituted monovalent hydrocarbon radicals, hydroxyaryl ethers joined to the t-butyl-substituted hydroxyaryl radical through the ethér l.inkage, hydroxyarylthioethers joined to the t-butyl~substituted hydroxyaryl radical through the thioether linkage and hydroxyaryl-methylene ethers jointed to -the t-butyl ~, , ~ % ~ 60SI-121 substituted hydroxyaryl radical throuyh the methylene e-ther linkage; R" is selected from the class consisting of lower alkyl radicals having one to five carbon atoms, e.g., methyl, ethyl, propyl, butyl, pentyl, etc. radicals; cycloalkyl radicals having five to seven carbon atoms in the ring, e.g., cyclopentyl, cyclohexyl, cycloheptyl, etc. radicals;
mono~nuclear and binuclear aryl radicals, e.g., phenyl, naphthyl, diphenyl, etc. radicals; mono-nuclear aryl lower alkyl radicals, e.g., benzyl, tolyl, xylyl, phenylethyl, etc. radicals and halogenated derivatives of the above radicals.
Although any methylalkylpolysiloxane fluid within the scope of formula (1~ is applicable in the process of the present invention, it is preferred that the fluid have a viscosity of from about 25 centistokes to about 100,000 centistokes when measured at 25C.
The t-butyl-substituted hydroxyl aryl methyl higher-alkyl polysiloxane polymer described above is the preferred methyl higher-alkyl polysiloxane polymer for utilization as a silicone lubricant. Preferably, the t-butyl-sub-stituted hydroxyaryl radical is present in the polymer chain so as to retard any oxidation of the lubricant fluid.
Although a methyl higher-alkyl polysi]oxane polymer may be utilized without such a t-butylsubstituted hydroxyaryl radical for anti-oxidation purposes in the preferred silicone lubricants o~ the instant case, i-t is desired to have such a substituent group in the higher-alkyl polysiloxane lubricant composition. The preparation of the methyl higher-alkyl polysiloxane polymers is more fully described in ~.S. Patent No. 3,669,884 dated June 13, 1972.
Accordingly, it is not necessary to go into any detailed process about the preparation of such fluids since if any more details than -that given above are needed as to the preparation of such methyl higher-alkyl polysilo~ane polymers with or without the t-butyl substituted hydroxyaryl radical, reference should be made to the foregoing Wright 3,669,884 dated June 13, 1972. As stated previously, for such methyl, higher-alkyl polysiloxane polymers when such polymers are utilized to lubricate either ha.rd metals or soft metals the foregoing chlorinated benzoate and phthalate additives of the Agens U.S. Patent 2,837,482, dated June 3, 1958, are not needed, as long as the chlorinated phosphites, chlorinated phosphona*e additives of the present case are present. It should be noted at this juncture that the foregoing chlorinated phosphites and chlorinated phosphonates of the instant case are not disclosed as substituent additives for the foregoing chlorinated benzoates and chlorinated phthalates of the foregoing Agens U.S. Patent 2~837/482 dated June 3, 1958.
The phosphites and phosphonates of the instant case improve the antiwear and lubricating properties for soft metals of silicone lubricants considerably more efficiently and at a higher level than is the case when the chlorinated benzoates and chlorinated phthalates of -the foregoing ~gens U.S. Patent No. 2,837,482 dated June 3, 1958 are utilized.
There are also other well known silicone polymers that may be utilized as silicone lubricant.s. Without mentioning -~ these polymers in detail, it is suffice to state that the instant chlorinated phosphites and chlorinated phosphonate additives of the instant case are superior imparting anti-`~

L2~
wear properties for soft metals to such lubricants than has been the case when such polymers have been utilized without any addltives or have been utilized with any of the prior art additives. Accordingly, with any of these silicone polymers that are utilized as lubricants, there may be utilized from .01 to l part by weight of a chlorinated phosphite or phosphonate. Although any chlorinated phosp-hite or phosphonate may be utilized, the most preferred that have been found suitable for most silicone lubricants and more specifically for the silicone lubricants mentioned above is tris-chloroethylphosphite and bis-chloroethyl-chloroethylphoshonate. It should be noted that it has been theorized that the trischloroethylphosphite changes to a bis-chloroethyl phosphonate after the passage of time and the two compounds are in equilibrium with each other. It has been postulated that these two compounds are the most effective antiwear additives for the fore-going silicone lubricants with respect to soft metals, such as, copper, brass or bronze. ~lthough less that .01 parts may be utilized, that is, even a slight trace of the instant phosphites and phosphonates will impart antiwear characteristics to a silicone lubricant, nevertheless it is felt that .01 parts by weight of the chlorinated phosphite or phosphonate are needed per lO0 parts by weight of the ` linear organopolysiloxane polymer for the phosphite or phosphonate to impart to the silicone lubricant sizable antiwear properties for soft me~als.
Further, evsn though more than one part by weight of the chlorinated phosphite or phosphonate could be utilized, generally such an excess amount may not be soluble in the silicone lubricant, thus negating its effectiveness as an antiwear additive. Preferably, 0.2. to 0.6 parts of the chlorinated phosphite or phosphonate is - l7 -., , "
, . . .

~OSI-121 utilized per 100 parts of the essentially linear organo-polysiloxane polymer. Chlorinated phosphites and phosphon-ates are sold by Mobil Oil Company, Monsanto Chemical Company and Berg Warren Corp., as well as many others.
These phosphites and phosphonates are generally produced by reacting ethylene chlorohydrin with P c13. The phosphonates are formed spontaneously by Arbuzov rearrange-` ment.
The above preparation for the foregoing phosphites and phosphonates is only meant to be exemplary, such materials being manufactured and sold by the foregoing companies listed above. Accordingly, it is not necessary to go into any further details as to their preparation.
Again, as stated previously, although the foregoing chloroethyl phosphites and phosphonates are the most preferred in the instant application, any other chlorinated alkyl phosphites and phosphonates may be utilized as ad-ditives in the lubricants of the instant case. In the examples below various additives were added to different organopolysiloxanes intended as lubricants. These mixtures were then tested for their lubricity properties on a Shell four-ball tester which comprises a device for holding three rigidly clamped one-half inch metal balls in a metal cup.
A further rotating ball of the same diameter is then pressed to contact with the three stationary balls by an adjustable floating arm and allowed to run for 1 hour. The contact points on the three stationary balls shows a circular scar ~ as wear progresses. The average diameter of these scars ; in millimeters after a 1 hour run at some particular speed and load is taken as the measurement of wear. The tem-perature at which the test is conducted may also be varied from room temperature to elevated temperatures of the order of about 150C. All balls are immersed in the lubricant fluid during the test. The type of metal employed in khe balls can be changed as, for example, lubricating surfaces can be steel-on-steel or steel-on-brass or brass-on-steel.
In the examples below, in all tests there was a 40 kill-ogram load on spinning ball which was made of bronze and in which the lubricant was maintained of a temperature of 167F. The center ball in which the load was rotated for 1 hours in the test in each case at a rotation of 1200 rotations per minute. The other balls were construc-ted at 25/100 tool steel. The sliding friction was also measured during each test. The examples below are given for the purpose of illustrating the reduction to practice of the instant invention and are not given for any purpose in limiting the definition and scope of the instant specification and claims. All percentages and parts are by weight.
` ~ In all of the test results tabulated below, there was utilized as the basic lubricating fluid, a fluid identi fied as Fluid X in the table below, which Fluid X is a linear polysiloxane having a 50 centipoise viscosity at 25C and was a methyldecyl substituted polysiloxane polymer ' having trimethylsiloxy terminal groups which has 1 - 3%
' coupled into it of t-hydroxyphenyl units. All the per-centages in the table are by weight of the additives ` added. The test are previously stated was carrled out in a Shell 4-ball tester which was run with a 40 killogram load on the rotating ball which was made of 25/100 steel and rotated at a rotation of 1200 rotations per minute for 1 hour while impinging on the three balls constructed ~` of bronze all of which balls were immersed in the Fluid X.
The amound of the additives added is indicated in the table ~ .
., -- 1 9 , .

- - :

60SI~121 29~
below in which the lubricant and additives mixture was maintained at a temperature of 167F for the 1 hour length of the test. Results of the tests are as follows:

Lubricant Wear Scar SL
Fluid X 1.7 mm Rose To 0.15 Fluid X + 4% dibutylhexyltetra-chlorophthal-ate 0.84 mm 0.05 Fluid X ~ 0.5~ tris-chloroethyl-phosphite 0.82 mm 0.05 Fluid X + 0.2~% tris-chloroethyl-phosphite 0.93 mm 0.05 Fluid X + 1.0% tris-chloroethyl phosphite 0.84 mm 0.05 '.
In addition, other conventional additives were tries.
These failed completely.
Fluid X + dialkyl zinc dithio-phosphite 2.6 rose to 1.7 Fluid X " dibutyl tin sulfide 2.4 rose to 1.5 As noted from the results set forth in Table 1 above, the instant phosphite and phosphonate additives were much more effective as antiwear additives for soft metals than were other conventional additives which failed com-pletely and were at l/~th the concentration just as effective as the dialkyltetrachlorophthalates as antiwear additives for soft metals. It should be noted that the instant phosphites and phosphonates as the above xesults in Table 1 indicate, even in trace amounts that is at a concentration of 0.25 weight percent in the methyl hi~her-alkyl fluid markedly improved the antiwear properties of ~-~

said methyl higher-alkyl fluid toward soft metals as indicated above. Accordingly, at the same concentrations the chlori-nated phosphite and chlorinated phosphonate additives of the instant case are the most effective additives for org-anopolysiloxane polymers as far as optimizing the antiwear properties of silicone lubricant polymers than is the case with prior art phthalate and benzoate additives and other prior art additives for this purpose.

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Claims (14)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1, A silicone lubricant composition consisting essentially of 100 parts by weight organopolysiloxane having a viscosity varying from 25 to 100,000 centipoise at 25°C. wherein the organo groups are selected from the class consisting of monovalent hydrocarbon radicals and halogenated hydrocarbon radicals with from 0.01 to 1 part by weight of a chlorinated compound selected from the class consisting of tris-chloro-ethylphosphite and bis-chloroethylchloroethyl phosphonate and mixtures thereof.

2. The composition of claim 1 wherein the organo-polysiloxane is a dimethylpolysiloxane.

3. The composition of claim 1 wherein in the organo group of said polysiloxanes are selected from the class consisting of methyl, chlorophenyl, tetrachlorophenyl and trifluoropropyl and mixtures thereof.

4. The composition of claim 1 wherein the organo-polysiloxane has the formula:

(CH3)n(R)m(R'(CH2)3)p(R")qSiO(4-n-m-p-q)/2 wherein in R is an alkyl radical containing from 6 to 20 carbon atoms, R' is a t-butyl-substituted hydroxyaryl radical that has the formula:

where Y is a member selected from the class consisting of hydrogen, alkyl radicals of 1 to 8 carbon atoms and hydroxyaryl radicals, where R" is selected from alkyl radicals of 1 to 5 carbon atoms; n has a value of from 0.50 to 1.95; m has a value of from 0.50 to 1,0; p has a value of from 0 to 0.5; q has a value of from 0 to one-fourth (m + n + p) and the sum of m + n + p + q has a value of from 2.002 to 3Ø

5. The composition of claim 1 wherein the organo-polysiloxane is a linear polysiloxane with an organo to Si weight ratio that may vary from 1.9 to 2.67.

6. A process for lubricating a metal surface selected from bronze, copper, tin, and lead consisting essentially of applying to the metal surface a silicone lubricant composition having 100 parts by weight of an organopolysiloxane wherein the organo groups are selected from the class consisting of monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals having a viscosity varying from 25 to 100,000 centipoise at 25°C. with from 0.01 to 1 part by weight of a chlorinated compound selected from the class consisting of tris-chloroethylphosphite and bis-chloroethylchloroethyl phosphonate and mixture thereof.

7. The process of claim 1 wherein the organopoly-siloxane is dimethylpolysiloxane.

8. The process of claim 6 wherein the organo groups in said polysiloxane are selected from the class consisting of methyl, chlorophenyl, tetrachlorophenyl and trifluoropropyl and mixtures thereof.

9. The process of claim 6 wherein the organopoly-siloxane has the formula:
(CH3)n(R)m(R'(CH2)3)p(R")qSiO(4-n-m-p-q)/2 wherein R is an alkyl radical containing from 6 to 20 carbon atoms, R' is a t-butyl substituted hydroxyaryl radical that has the formula:

where Y is a member selected from the class consisting of hydrogen, alkyl radicals of 1 to 8 carbon atoms and hydroxyaryl radicals, R" is selected from alkyl radicals of 1 to 5 carbon atoms; n has a value of from 0.50 to 1.95; m has a value of from 0.50 to 1.0; p has a value of from 0 to 0.5; q has a value of from 0 to one fourth (m + n + p) and the sum of m + n + p + q has a value of from 2.002 to 3.0

10. The process of claim 6 wherein the organopoly-siloxane is essentially a linear polysiloxane with an organo to Si weight ratio that may vary from 1.9 to 2.67.

11. A silicone lubricant composition consisting essentially of 100 parts by weight of an organopolysiloxane having a viscosity varying from 25 to 100,000 centipoise at 25°C. wherein the organo groups are selected from the class consisting of monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals with from 0.01 to 1 part by weight of a chlorinated compound selected from the class consisting of tris-chloroethylphosphite and bis-chloroethyl-chloroethylphosphonate and mixtures thereof with from 1 to 10 parts by weight of a compound selected from the class consisting of a chlorinated phthalate and a benzoate and mixtures thereof.

12. The composition of claim 11 wherein the chlorinated phthalate is selected from the class consisting of bis-2-ethylphenyl tetrachlorophthalate, bis-2-butylethylhexyl tetra-chlorophthalate, octyltetrachlorobenzoate and dioctyltetrachloro-phthalate.

13. A process for lubricating a metal surface selected from bronze, copper, tin and lead consisting essentially of applying to the metal surface a silicone lubricant composition having 100 parts by weight of an organopolysiloxane wherein the organo groups are selected from the class consisting of monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals having a viscosity varying from 25 to 100,000 centipoise at 25°C. with from 0.01 to 1 part by weight of a chlorinated compound selected from the class consisting of tris-chloro-ethylphosphite and bis-chloroethylchloroethylphosphonates and mixtures thereof with from 1 to 10 parts by weight of a compound selected from the class consisting of a chlorinated phthalate and benzoate and mixtures thereof.

14. The process of claim 13 wherein the chlorinated phthalate or benzoate is selected from the class consisting of bis-2-ethylhexyl tetrachlorophthalate, bis-2-butylethylhexyl tetrachlorophthalate, octyltetrachlorobenzoate and dioctyl-tetrachlorophthalate.